Production of valuable products from methane gases



1940. H. WATERMAN ErAL 2,221,658

PRODUCTION OF V-ALUABLE PRODUCTS FROM METHANE GASES Filed Aug. '7, 1959 Mefhdne Space Velocitq Uniis m m Inventor-51min Israel Waterman Willem Jm Hessels Dirk Willem van Krevelcn 5g fheir Arfornag UNITED STATES PATENT "orrlcs PRODUCTION OF VALUABLE PRODUCTS FROM METHANE GASES Hein Israel Waterman, Willem Jan Hessels, and Dirk Willem van Krevelen, Delft, Netherlands, assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application August 7, 1939, Serial No. 288,818 In the Netherlands August 23, 1938 7 Claims.- (Cl. 260673) The present invention relates to the produc- CaliforniaColusa, Fresno, Kern, Solano,.Sutter tion of valuable products from methane-contain- Counties ing gases. More particularly, the invention re- Kansas-Montgomery County lates to the production of benzol, ethylene, acet- Texas-Gulf District I ylene, and other valuable hydrocarbon products Alabama-Choctaw, Clark, Fayette Counties 5 from methane. ArkansasCrawvford, Jefferson Counties Methane is available in enormous quantities in I1lin0isBureau, Crawford Counties natural gases. Natural gases, by which term is MississippiAdams, CoVingtonL-Jackson Counties meant those hydrocarbon-containing gases which Montana-Chduteau, Fallon, Teton Countie originate from and are associated directly or in- North DakotaLa Moure County I 10 directly with crude petroleum, are composed pre- OklahomaCotton, Osage Counties dominantly of methane and ethane, sometimes UtahGrand County I with smaller quantities of propane, butane, pentane and lesser amounts of higher hydrocarbons i g i g 2353 95 2 i ggf figgg ggg gsgf 1.3 and inorganic gases, such as CO2, N2, HzS, etc. tainin methane and ethane A the a 1 se from such natural gases as contam propane butane the m thane areas in which methane i s th e only and/or pentane' are called Wet s These combustible component, contain no higher hy- Wet gases aretqmte valuableismce propane drocarbons, they are of no value for the recovery tane and pen ane are much m demand d can of natural gasoline products. In certain areas 90 be profitably Y from these gases even .where these drygases are available near induswhen present, m m Small amounts Propane trial centers, a cer, ain amount can be disposed of for m 15 readily dehVdrPgEna'ted to propyl' to supply the industrial and domestic needs at Wh.1ch m tun} 1S ntuch m demand for the a relatively high return. In a few of the areas productlon of any} chlonde any] alcohol glycer' where the supply greatly exceeds the commercial 2.) ol, solven liquefieq petroleum gas fuels demand for pipeline use, large amounts are frigerants and, especially, for the production of burned in the production of carbon black high anti'knock m fllkylaum? with gas used for the production of carbon black in amns' Butane hkewlse isomenzed to 304311 the Panhandle area alone has been as high as q g h z g' and is one billion cubic feet per day. Gases containing 1111.10 deman q ese pmduc s are an appreciable quantity of ethane are preferred i m large quanmles m the production of for this purpose. Notwithstanding the amount of avlanon gasolme many *1 products these dry gases used for pipeline use and the Wet gases therefore mvanably treatefi t large amount used for carbon black production, remove these valuable l i' This 15 larger quantities of these gases, especially those usually done by compressl-on 'absorptlon' or containing only methane, are blown into the air sqrptlon processes After the removal of the or burned in fiambeaus, as there is at present no higher hydrocarbons from the wet gas, the gas outlet except at prohibitive costs cqnslsts ptedommalitly of methane or mefltane In view of the enormous quantities of methane 40 rgfg ggg i ifig gi f g si fisg .2;: in these gases, for which there is at present no of gaggg i g i x ii??? l; ggzg gz g ifiggig converting this methane into utilizable products. in exceedingly large quantities I Numerous processes have been worked out where- 1; Aside from the large quantities of stripped or by methane may be converted m o valuable or ganic chemicals. These rocesses are, however, artlficlany dned gases m from the treat capable of utilizing only a small portion of the ment of wet gases there are even larger quan enormous quantities of gas available. titles of naturally-occurring dry gases composed of mixtures of methane and ethane. There are, Desplte the fact that the decomposmon of methane is thermodynamically complete at a )0 E f large fields m the soca'ned temperature of about 850 C., it is an exceedingly 0 metpane areas ch y eld gas in which meth stable compound. Whereas, all hydrocarbons, ane Is h only P such with the exception of methane and ethane, are fields are found mrmstance m thermodynamically unstable at temperatures LouisianaCaddo Barish, De Soto Parish above about 200 C., methane can be used as an 55 lowing table:

about 900-1000 inert diluent in the pyrolysis of benzene at 700 C. The thermal decomposition of methane starts very slowly at temperatures of about 650-700 C.

and becomes appreciable only at temperatures of 0., providing the time of heating is sufficiently long. This is shown in the fol- The thermal decomposition of methane generally proceeds to the formation of carbon and hydrogen according to the reversible reaction:

out-( mm At elevated temperatures this reaction tends to go to substantially complete decomposition of the methane. Thus, the equilibrium mixture contains:

0.36%methane at 1200 C., 1.1% methane at 1000 C. and 2.5% methane at 850 C.

Franz Fischer, Brennstofi Chem. 9 309-316 (1928) and Brennstoff Chem. 13 (1932) found chiefly of aromatic character.

thatv if methane is subjected to temperatures in the order of 1,000 C. to 1,300 C. for much shorter times, the decomposition can be arrested before the reaction, according to the above equation, is completed. Under suitable conditions unsaturated residues, such as methyl radicals,-

ethylene, acetylene, are formed which polymerize or condense under the reaction conditions to give substantial yields of higher hydrocarbons,

The various factors involved in this method of converting methane into valuable liquid hydrocarbons were carefully investigated and the following generalizations found:

IL-The thermal treatment of methane for I short contact times leads to the production of hydrogen, ethylene, acetylene, a light oil consisting largely of benzene, a heavy oil or tar consisting mainly of high aromatic hydrocarbons,

. and carbon.

2. The contact time and the temperature are equally important and interrelated factors.

3. The temperature-time relation is a straight line function which can be expressed by a mathematical equation.

4. Generally speaking, contact times greater than one second lead to low yields of desirable products and high yields of carbon.

5. By increasing the temperature the contact timemay be decreased. By so doing the yields of products, however, are gradually shifted, so that at the higher temperatures the yield of acetylene is increased at the expense of the yield of benzol.

6. Maximum yields of liquid hydrocarbons are obtained at temperatures between about 1,000 C. and 1,300 C.

7. The maximum yields are obtained under conditions at which about 20-30% of the methane is decomposed.

8. The maximum yield of low boiling hydrocarbons obtainable from methane by the process is about 0.3 gallon per thousand cubic feet. This is the most practical of the various processes suggested for the utilization of methane gases and is the only process so far found which appears capable of profitably utilizing any substantial quantity of the available dry gas. Although the process has been repeatedly studied and has been applied on a semi-technical scale, the yields of low boiling hydrocarbons (about 0.3 gallon per thousand cubic feet) are quite low and the process has not attained widespread application.

According to the present invention the conversion of methane to the more valuable hydrocarbons is effected by an induced reaction under difierent conditions. In order that our contribution in this field may be clearly understood and appreciated, it is necessary to devote special attention to the time factor. In the investigations of Franz Fischer and later investigators, the methane was passed at a suitable velocity through a tube or other reaction chamber of known volume heated externally by any suitable means to the desired reaction temperature. Knowing the volume of the reaction chamber, the temperature, and the weight of methane treated in any given time, previous investigators have attempted to calculate the time of reaction and have reported the results of these computations as the contact time (or space velocity) at which the methane was treated. Thus, for instance, if 90 grams of methane were passed in five hours through a reaction zone of c. 0. volume, (i. e. 5 c. c. of the reactor space assumed to be within the arbitrarily fixed temperature limits) heated to 1,200 C., the contact time has usually been calculated as follows:

0.132 second Such calculations give purely arbitrary figures which may be properly employed in comparing results of a series of comparative experiments, but are clearly no indication of the true average contact time. Thus, while all investigators agree that the contact time is extremely important and must be closely adjusted at any given temperature to obtain a certain result, equivalent results obtained by different investigators at the same temperature are claimed to be obtained at widely different contact times. This is due to the impossibility of accurately calculating the average time of contact in this crude manner. Under the conditions employed, the temperature of the reaction vessel is difficult to determine accurately, and the volume of the reaction vessel which is at temperature can only be very roughly approximated. Furthermore, the volume assumed for that portion of the reaction vessel which is at temperature depends upon an arbitrary choice of allowable temperature difference. Furthermore, under the conditions employed, all of the gas is not evenly heated to the maximum temperature (measured on the outside of the reaction vessel), and the volume of gas at the reaction temperature, calculated according to the gas laws, may be considerably in error.

The contact time, furthermo're, depends upon the character of the inner and outer surface of the reaction chamber, the heat conductivity of the reactor material, the dimensions of the reactor, the presence of diluents in the gas treated, the amount of expansion of the gas volume during reaction, etc. As a result of all these various factors, the contact time, calculated as above shown, cannot be expected to indicate the true mean contact time, nor to be comparable with different apparatus, operators, etc.

In order to clearly indicate the conditions which We have found more advantageous for the execution of the present process, the true contact 7 time is hereinafter expressed in terms of an arbitrary unit called the methane space Velocity unit. If methane is passed at a very fast rate through a reaction tube heated to a given temperature, no appreciable reaction takes place.

If the rate of throughput (calculated from the weight of methane applied per unit of time) is gradually decreased, a definite and easily recognizable point is reached at which the decomposition of the methane is visually apparent by the beginning of the formation of a slight fog. The fog or mist is probably due to traces of tar which have been shown to be invariably formed in the thermal decomposition of methane. This space velocity at which methane gives the first visual indication of decomposition (as seen in the issuing gas) at a temperature of 1000 C., and essentially atmospheric pressure is arbitrarily designated as one methane space velocity unit. If this space velocity (or contact time) is designated as one methane space velocityunit, then it is found that at temperatures of 1065, 1120, 1210, etc. the methane space velocity units at which decomposition of the methane is first visually noticed are 3.3, 9.4, and respectively. If the logarithms of the methane space velocity units are plotted against the temperatures in degrees centigrade, the points fall essentially on a straight line. This line, which indicates the respective conditions of space velocity and temperature at which the decomposition of methane is first visually noticed, is shown as line A-A' in the accompanying graph. Thus, under all conditions falling above and to the left (at higher temperatures and lower space velocities) of line AA, methane is pyrolyzed, and, under all conditions falling below and to the right (at lower temperatures and higher space velocities) of line A-A', the pyrolysis of methane practically does not take place.

The line B-B' in the accompanying graph represents the conditions of temperature and space velocity (expressed as methane space velocity units) at which methane is thermally decomposed to an extent of 15%. Since in previous investigations the conditions for the best yields have always been severe enough to react at least 15% of the methane, it is obvious that these conditions are confined to that area above the line B-B", and most certainly above the line A-A'. Thus,

' Smith, Grandone and Hall, who made a careful study of the Fischer process, (U. S. Bur. of Mines Rept. R. I. 3143, and Nat. Pet. News, page 69, Oct. 28, 1931), claim that the optimum yield of benzene is obtained when, at a given temperature, only sufficient time is allowed for approximately 25% by weight of the methane to be decomposed (U. S, Pat. No. 2,061,597). These con ditions would be represented on the accompanying graph by a line approximately parallel to and above line BB'.

We have found that methane may be converted to benzol and other valuable hydrocarbons by an induced reaction under different conditions with an equally good yield of liquid hydrocarbon products and a much greater production rate.

A-A, such, for example, as those represented in the area between lines the accompanying graph.

In the presence of certain inductors and under otherwise suitable conditions, methane may be induced to react to give excellent yields of benzoland other valuable hydrocarbons under conditions considerably less severe than those generally required to effect an appreciable amount of reaction of methane. The property of inducing the formation of benzol and valuable hydrocarbons from methane, we have foundyis possessed by a large number of thermally less stable com-- pounds. One group of compounds which we have found to be very effective is, for instance, the higher aliphatic hydrocarbons. The eiTectiveness of these compounds is, in general, somewhat dependent upon the ease with which they are thermally decomposed and, hence, upon their molecular weight. Thus, for example, ethane, which is nearly as thermally stable as methane, is not an inductor; propane may act as an inductor if used in sufficient quantities under favorable conditions; butane is a fairly good inductor; and saturated and unsaturated aliphatic hydrocarbons having four or more carbon atoms are the best inductors. While it is known that methane containing an appreciable quantity of ethane produces a greater yield of liquid hydrocarbons than pure methane, these results are obtained under conditions more severe than those.

represented by the line A-A' and are not in any way connected with the phenomena of induced methane conversion. The yields of lowboiling liquid hydrocarbons cbtainablefrom the thermal treatment of aliphatic hydrocarbons is known to be much higher for the hydrocarbons higher than methane. Thus, for example, the following yields of low boiling liquid hydrocarbons may be obtained per thousand cubic feet of the vapors of the following pure hydrocarbons:

The inductive action of a few of the many applicable aliphatic saturated and unsaturated hydrocarbons is illustrated in the following examples.

EXAMPLE 1 To an industrial, dry methane gas containing 91.3% methane, 5.1% nitrogen, 0.2% higher hydrocarbons, 3.4% hydrogen ancltraces of other gases, there was added 4.75% by volume of a commercial butane'fraction. Upon passing the mixture (eo'ntaining 4.55% butane) through a reaction tube maintainedat 1170 C. at a rate of 53 methane space velocity units, 4.25% of the methane applied was induced to react. In the absence of the added butane, the methane gas undergoes substantially no change upon being subjected to the same treating conditions.

EXAMPLE 2 3.33% by volume of ethylene was added to a dry methane gas. Upon passing the gas mixture through a reaction tube maintained at 1170 C. at a rate of 62 methane space velocity units, only about 1% of the methane was induced to react. It is, therefore, seen that ethylene exerts only a very slight inductive action.

EXAMPLE 3 EXAMPLE 4 3.33% by volume of benzene (CsHs) was added to a dry methane gas. Upon passing the gas mixture through a reaction tube maintained at 1170 C. at a rate of 54 methane space velocity units, no reaction of the methane was detected. Thus, it is seen that benzene has no inductive action and that methane does not react under the prevailing conditions.

EXAMPLE 5 2.56% by volume of butadiene was added to a dry methane gas. Upon passing the gas mixture through a reaction tube maintained at 1170 C. at a rate of 48 methane space velocity units, 8% of the methane was induced to react. This is illustrative of the inductive action of the higher unsaturated aliphatic hydrocarbons.

Another group of compounds which we have found are capable of inducing formation of liquid hydrocarbons from methane under conditions less severe than those represented by the line A-A are the halogenated hydrocarbons, such, for example, as CH3C1, CHzClz, CHCla, CC14 and the halogenated derivatives of ethane, propane, butane, pentane, ethylene, propylene, butylene, amylene, toluene, and the like higher hydrocarbons.

The use of halogenated hydrocarbons as inductors in the treatment of dry methane gas by induced reaction is illustrated by the following examples:

self by introducing a small amount of chlorine or bromine into the methane gas being treated, either prior or during reaction. This is illustrated by the following examples:

Example number Inductor employed None Ch Bra Amount of inductor. percent by volume 10. 7. 7 Temperature C... 1165 1169 1170 Space velocity in methane units 44 44 57 Methane induced to react ..pereent EXAMPLE 16 3.5% by volume of dimethyl sulfide, (CH3)2S, was added to methane. Upon passing this mixture through a reaction tube maintained at 1170 C. at a rate of 56 methane space velocity units, 7% of the methane was induced to react. No appreciable reaction is noticed under these conditions in the-absence of an inductor.

The ability of certain materials to induce-methane to react, within a limited range of conditions under which methane is normally stable, is quite surprising. Although experimental evidence indicates that the mechanism of the induced reaction is not the same for all inductors, and that the halogenated inductors react in a different manner than the higher hydrocarbons, the present invention is not limited whatsoever to the soundness or accuracy of any theories, and no attempt is herein made to explain the mechanism of the reaction or reactions involved. Compounds known to form free radicals, such as tetraethyl lead and sodium vapors, were found to ex- Example number Inductor employed None CHzCl 0131C]: CHCI: CO1; C2H5Cl CzH4Clz Amount 01 inductor percent by volume 0 9. 6 5. 2 4. 9 1. 96 2. l 5. 9

Temperature 0.. 1165 1169 1171 1169 1169 1172 1170 Space velocity in methane units. 44 55 53 49 68 54 59 I Methane induced to reaet percent. 0. 05 6 10 13 7 6. l 9. 5

The halogenated hydrocarbons, if used, may be applied as such or may be formed directly in a preheating chamber or the reaction chamber itfollowing examples showing the results ofexperiments made by passing a dry methane gas containing varying amounts of inductor through a heated reaction tube under conditions at which methane is not normally aflected.

decomposition. This is illustrated by the folio ing examples showing results of experiments on Example number 5 17 is I 19 2o 21 22 2a Inductor employed .Q None CHzCh CHQCI: CHaClz CHaCl GH3C1 CHgCl Amount of inductor percent by volume. 0 0.83 2 5 9. (l 33 76 Temperature 0.. not 1170 1170 1170 1169 ,1162 1162 Space velocity in methane units 44 56 51 56 55 61 54 Methane induced to react-percent" 0 4 8 8 6 0 0 The allowable limits of concentration of inducthe conversion of methane in the presence of tor which may be employed in the methane treatinductors at several temperatures. ed to induce the reaction of methane according to the present invention, depends somewhat upon the particular inductor employed and upon Dump 16 number 20 various factors, such as the reaction conditions, 24 25 26 27 the amount of inert diluent, if any, in the methane and may Vary considerably In Inductoreinployed CQHQO] 0 11 01 C,H5C1 OQHGCI general, the concentration of inductor is between Amount of inductor 25 about and 12% and preferably between about Temperatur i 1% d 10%, igitcgavlcelocity zritrenietgianc gnitsd 54 64 62 62 The inductor may be added to the methane gas reaction??? .Xfreffh. 6.1 so 7 2.8 either prior to or during the reaction in any convenient manner such, for instance, as by contaot- From these examples, it is seen that under 30 ing the methane gas with the liquld indllCtOr conditions Where pyrolysis of methane takes maintained at a suitable temperature. In the place in the absence of an inductor (Example case of gaseous inductors these may be added di- 2'7), the induced reaction does not take place to rectly to the gas stream in the requisite quantiany practical extent. Under conditions where ties. Aside from directly adding a higher alithe best yields of liquid hydrocarbons are formed phatic hydrocarbon to dry methane gas, excellent P normal h m treatment methane the mixtures of methane gas and higher hydrocarbon 2g??? igg g ififg gg z g g g gg g I ace Inductors maybe.btamed.dlr ectly P recovfa-ry velocity, methane may be converted by induced plants (compression, adsorption, and absorption reaction at temperatures up to about 13000 c. plants) by simply adjust g the recovery process Since, however, even with the most favorable 50 that the pp artificially dried exit gas space velocity, considerably higher yields of contains the desired concentration of higher hygaseous hydrocarbons are formed at the expense drocarbons. Another excellent way of preparing of the yields of liquid hydrocarbons, the process suitable mixtures of methane and hydrocarbon is preferably e u e t t mpe atures below inductors is to blend the dry methane gas with about 1210 a Suitable proportion of when halm In order to induce the reaction of methane genated hydrocarbons are used as inductors the fifi zg g ig i gii 'g 2522 1? ig gi i actual consunjlptlon of m? may be quite velocity. This maybe done, in general, down to small. Thus, if ethyl chloride is used, for exam- 3 temperature of about 10000 C. Below about Die, the HCl liberated during the reaction may be 1000 C. the induced reaction cannot be made recombined with the ethylene which is also to take place to any appreciable extent. Thus, formed to a certain extent during the reaction, when passing methane containing 12.5% of and reused. In this way the ethyl chloride may C2H5Cl through a reaction tube heated to 900 C. be recycled in t process at a rate of 2 methane space velocity units (cal- As mentioned above, the phenomena of culated contact time 1.7 sec.) no induced reduced methane reaction is found to take place actlon of methanei was observed only within a limited temperature range. For The spaeevelocliy fcontaciitlme) 0f the rnethth k f ane-containing feed 1s so ad usted, according to 8 8a 6 0 companson expenmfemfs Whelem the present process, that at the temperature cmthe temperatures employed were Wlthm the ployed, the conditions are not sufiiciently severe ferred wn e Of 1160 to 1180 e to effect any appreciable thermal decomposition chosen for the foregoing examples. While, in of methane, i. e. below the line A-A'. Surprisgeneral, the induced reaction is most pronounced ingly enough, it is found that if the Conditions within the temperature range of about 1100 C. to 1210 C., the induced reaction of methane may be effected at somewhat higher and lower temperatures if the space velocity is properly adjusted. As the temperature is raised while the space velocity is maintained constant, the amount of methane reacted by induced reaction decreases sharply as soon as the conditions become sufficiently severe to cause normal thermal.

' about 1000 methane units.

ane, the yield of liquid hydrocarbon is, in general, increased. At space velocities higher than necessary to provide the necessary conditions for induced reaction, the yield of total products is, in general, lower and the percentage of gaseous products, particularly ethylene, in the product is higher. This is illustrated by the following examples showing the results of experiments on the treatment of a methane gas, to which 1.65% by volume of octane was added, at 11.70" C.

Example number Space velocity in methane units 74 06 58 49 Gaseous reaction products in the product percent 55 53 50 47 Non-gaseous reaction products in the product percent. 45 47 50 53 Relative total yields of products. .75 .78 .90 1.00

For the temperature range of 1000 C. to 1300 C. the space velocity may vary from about 2 to For the more preferred temperatures of from about 1100 C. to 1210 C. the space velocity is usually between about 6 and about 250 methane units.

Under the above-described conditions of temperature and space velocity, which we have found applicable for the induced reaction of methane, the percentage of the total applied methane which undergoes reaction (the conversion) is usually less than about 15% and usually varies between about 4 and 12% per pass, dependingupon the inductor employed, the concentration of the inductor, the reaction conditions, etc. Hydrogen, if present to an appreciable extent in the gas mixture to be treated, materially decreases the conversion of the methane but does not, in general, materially affect the relative proportions of gaseous and liquid products. Nitrogen and other inert gases, when present in large amounts in the gas mixture to be treated, decrease the conversion somewhat and may increase the proportion of acetylene in the product.

In the present process, as in the above-described normal pyrolysis of methane, the formation of liquid hydrocarbon products depends upon heating the methane for such short times that the normal decomposition to carbon and hydrogen is arrested before it can go to completion, and yet at times sufficiently long to allow the formation of liquid products by secondary reactions. To obtain the maximum yields of liquid products, very short and accurately controlled contact times must, therefore, be provided. Since, in order to maintain these optimum conditions, the conversion of methane per pass is, according to the present process, usually less than 15%, it is desirable and economical to subject the gaseous reaction product, preferably after recovering the non-gaseous reaction products, to one or more further treatments. Since, under the preferred conditions of the present process, the inductor is, in general, only about from about 50 to reacted in one pass through the reaction zone, it is not usually necessary to add further quantities of inductor when retreating the gases. In some cases the addition of further amounts of inductor may, however, be desirable. The retreatment of the once-treated gases not only allows the methane to be more completely reacted but also allows the unsaturated gases, (ethylene and acetylene) which are invariably formed, to be converted into more valuable liquid products. The results obtainable by retreating the exit gases (after separating the nongaseous products) are illustrated by the following examples:

EXAMPLE 32 A dry methane gas to which had been added 2.4% by volume of a mixture of hexane and heptane was passed through a reaction tube maintained at 1170 C. at a rate of 4'7 methane space velocity units, whereupon 9% of the methane was induced to react. The total product contained:

Percent Tar+carbon 23 Light boiling hydrocarbons (75% CsHs) 27 Ethylene 25 Acetylene 25 When the non-gaseous products were removed after each treatment and the gases retreated, a total of 24% of the methane was induced to react in five treatments. The total product contained:

Percent Tar and carbon 31 Light boiling hydrocarbons 49 Ethylene ",1; 8 Acetylene 12 Example number Amount of inductor. .percent by volume. 0 14. 2 3. 1 Analysis of feed:

Methane 85.8 90. 9

Propane... 0 7. 5 1.7

Butane... 0 6. 7 1.4 Temperature... 1170 1170 1170 Space velocity in methane units 57 57 57 Methane induced to react .perccnt.. About 3 12 20. 5

Analysis of the product: 1

Tar and carbon 30 21 Light boiling hydrocarbons. 30 45 Ethylene..... ll 11 Acetylene. l 14 20 Of the light boiling hydrocarbons formed, about 35% was formed in the first pass, 25% in the second pass, 15% in the third pass and 12% in the fourth and fifth passes. These experiments also illustrate the relatively weak inductive action of propane and the detrimental effect of excess inductor.

In many cases it will be desirable to remove some or all of these reaction products from the reacted gases. Thus, for example, the acetylene, which .is very valuable, may be removed and recovered by conventional methods and the ethylene may be converted into valuable liquid hydrocarbons by catalytic polymerization under pressure or by chemical treatment, such as alkylation, etc. If it is not desired to recover these unsaturated gases from the gaseous reaction product, the gases may be utilized for producing carbon black or hydrogen. Since these gases are equivalent, if not superior, to the original untreated gas for carbon black production, the

present process may be employed in conjunction with the production of carbon black and a more efficientutilization of the realized.

The present process may be applied to methane or methane-containing gases, including those containing methane with small amounts of other hydrocarbons and/ or inert gases. It is, however, especially applicable and advantageous for the methane thereby treatment of the large available quantities of .ing the induced methane reaction is distinctly more advantageous for the utilization of these gases than the hitherto proposed non-induced pyrolysis processes. Whereas the ordinary noninduced pyrolysis of methane gives the best yields of low boiling liquid hydrocarbons over a range of space velocities covering approximately 20 to 30% conversion of the methane, the present induced reaction gives the maximum yield of low boiling liquid hydrocarbons over a comparatively narrow range of much higher space velocities.

Thus, whereas at 1190 C. a maximum yield of low boiling liquid hydrocarbons is obtained in four passes by normal pyrolysis of methane at space velocities of from about 10 to about 18 methane units, an equal, or slightly better, yield of low boiling liquid hydrocarbons may be obtained, for instance, at 1190 C. and four passes by the induced reaction at space velocities of from about 38 to about 68 methane units. Thus, it is seen that by the present process an equal yield of low boiling liquid hydrocarbons may be obtained while the production capacity of the reactor is increased at least 300%.

We claim as our invention:

1. A process for the production of liquid hydrocarbon products from methane, which comprises subjecting methane in the presence of from 0.5 to 12 mol per cent of an aliphatic hydrocarbon containing at least four carbon atoms to a thermal treatment for a time corresponding to a rate of from 2 to about 1000 methane space velocity units and at a temperature below the temperature of the first visual decomposition of methane at the same space velocity, said temperature beingat least 1000 C. and not greater than 1300 0., whereby a portion of the methane is induced to react to give largely aromatic hydrocarbons. a

2. A process for the production of liquid hydrocarbon products from methane. which comprises subjecting methane in the presence of from 1 to 12 mol per cent of an aliphatic hydrocarbon containing at least three carbon atoms to a thermal treatment for a time corresponding to a rate of from 2 to about 1000 methane space velocity units and at a temperature below the temperature of the first visible decomposition of methane at the same space velocity, said temperature being at least 1000 C. and not greater than 1300 C.

whereby a portion of the methane is induced to react to give largely aromatic hydrocarbons.

3. A process for the production of liquid hydrocarbon products from methane, which comprises subjecting methane in the presence of from 0.5

to 12 mol per cent of a halogenated hydrocarbon to a thermal treatment for a time corresponding to a rate of from 2 to about 1000 methane space velocity units and at a temperature below the temperature of the first visible decomposition of methane at the same space velocity, said temperature being at least 1000 C. and not greater than 1300 C. whereby a portion of the methane is induced to react to give largely aromatic hydrocarbons.

4. A process for the production of liquid hydrocarbon products from methane, which comprises subjecting methane in the presence of from 0.5 to 12 mol per cent of a halogen derivative of ethylene to a thermal treatment for a time corresponding to a rate of from 2 to about 1000 methane space velocity units and at a temperature below the temperature of the first visible decomposition of methane at the same space velocity, said temperature being at least 1000 C. and not greater than 1300" C. whereby a portion of the methane isinduced to react to give largely aromatic hydrocarbons.

5. A process for the production of liquid hydro carbon products from methane, which comprises subjecting methane in the presence of from 0.5 to 12 mol per cent of a thermally less stable inductor to a thermal treatment for a time corresponding to a rate of from 2 to about 1000 methane space velocity units and at a temperature of from 35 to 85 C. below the temperature of the first visible decomposition of methane at the same space velocity, said temperature being at least 1000 C. and not greater than 1300 C., whereby aportion of the methane is induced to react to give largely aromatic hydrocarbons.

6. A process for the production of liquid hydrocarbon products irom methane, which comprises subjecting methane in the presence of from 0.5 to 12 mol per cent of a thermally less stable inductor to a thermal treatment for a time corresponding 'to a rate of from 2 to about 1000 methane space velocity units, and at a temperature below the temperature of the first visible decomposition of methane at the same space velocity, said temperature being from 1100 C. to 1210 C. whereby a portion of the methane is induced to react to give largely aromatic hydrocarbons.

7. A process for the production of liquid hydrocarbon products from methane, which comprises subjecting methane in the presence of from 0.5 to 12 mol per cent of a thermally less stable inductor to a thermal treatment for a time corresponding to a rate of from 2 to about 1000 methane space velocity units and at a temperature below the temperature of the first visible decomposition of methane at the same space velocity, said temperature being at least 1000 C. and not greater than 1300 C.,.whereby a portion of the methane is induced to react to give largely aromatic hydrocarbons.

HEIN ISRAEL WATERMAN.

WILLEM JAN HESSELS.

DIRK WILLEM VAN KREVELEN. 

